Fluoroadamantane derivative

ABSTRACT

Adamantane derivates which can be material compounds of a polymer excellent in etching resistance and having improved transmittance to light having a short wavelength, 
     represented by the formula (2A″) 
                         
wherein Y 1F  is a fluorine atom or a hydroxyl group.

TECHNICAL FIELD

The present invention relates to a novel fluoroadamantane derivative.More particularly, the present invention relates to a fluoroadamantanecompound having from one to four hydroxyl groups bonded to a tertiarycarbon atom in the fluoroadamantane skeleton (hereinafter referred to ashydroxyfluoroadamantane) and a compound having a hydroxyl group of suchhydroxyfluoroadamantane converted by an acrylic acid derivative.Further, it provides a process for producing such a compound employingliquid phase fluorination, and a novel intermediate for the productionprocess.

BACKGROUND ART

Non fluorine type adamantane derivatives are useful, in etching in whichphotolithography is applied, as e.g. a compound constituting an etchingresistant thin membrane material to protect the substrate layer.

As fluorinated adamantane derivates, (perfluoroadamantyl) acrylates anddiacrylates are disclosed in a document (see Patent Document 1).

Further, a process for producing 1-hydroxyperfluoroadamantane,2-hydro-1-hydroxyperfluoroadamantane and2-hydro-1,3-dihydroxyperfluoroadamantane by aerosol fluorination hasbeen reported (see Non Patent Documents 1 to 3).

Patent Document 1: WO03/55841

Non Patent Document 1: Adocock, James L. et al., Journal of OrganicChemistry, 1995, Vol. 60, p. 1999-2002.

Non Patent Document 2: Adocock, James L. et al., Journal of OrganicChemistry, 1996, Vol. 61, p. 5073-5076.

Non Patent Document 3: Adocock, James L. et al., Journal of OrganicChemistry, 1992, Vol. 57, p. 4297-4300.

DISCLOSURE OF THE INVENTION

Problems that the Invention is to Solve

Patent Document 1 discloses a chemical formula of acrylate ofperfluoroadamantane but there are no grounds for a method to obtain sucha compound or availability of such a compound. For example,1-hydroxyperfluroadamantane as a production material is hardlyavailable, and its preparation process and preparation examples are notdisclosed at all. Further, the present inventors have produced1-hydroxyperfluroadamantane, but no compound showing the spectrum datadisclosed in Patent Document 1 has been obtained.

Non Patent Documents 1 to 3 disclose a fluorination method by aerosolfluorination. This fluorination method is a means of bringing fluorinegas into contact with the surface of a solid substrate, and accordingly,the reaction will take place only at the surface of the substrate,whereby it is very difficult to achieve a high yield by this method.Particularly, fluorination of 1,3,5-trihydroxy form or1,3,5,7-tetrahydroxy form of perfluoroadamantane by the above method isexpected to be very difficult, and this method cannot be employed as anindustrial production process. Further, with respect to the trihydroxyform and the tetrahydroxy form, no practical preparation example hasbeen disclosed.

Means to Solve the Problems

The present inventors have conceived that a fluorinated adamantanederivative may be a material which is more excellent in transparency tolight having a short wavelength, which is more excellent in etchingresistance and which can be applied to microphotolithography, opticaladhesives, etc. Thus, they have found that a hydroxyfluoroadamantanewhich may be a material of such a derivative can be produced by anindustrially applicable process. More particularly, they have realized aprocess for producing a compound having a fluorinated adamantaneskeleton and having one to four hydroxyl groups bonded to a tertiarycarbon atom at the 1-, 3-, 5- or 7-position in the adamantane group, bya novel producing route employing liquid phase fluorination from anavailable compound having an adamantane skeleton. They have furtherrealized a process for producing a novel compound having both onefluorinated adamantane skeleton and one to four acrylic acid derivategroups, by reacting such a compound with an acrylic acid derivate.

Namely, the present invention provides the following.

1. A process for producing a compound represented by the followingformula (1), which comprises subjecting a compound represented by thefollowing formula (10) to esterification reaction with a compoundrepresented by the following formula (11) to obtain a compoundrepresented by the following formula (12), subjecting the compoundrepresented by the formula (12) to fluorination in a liquid phase toobtain a compound represented by the following formula (13), subjectingthe compound represented by the formula (13) to hydrolysis oralcoholysis to obtain a compound represented by the following formula(2), and reacting the compound represented by the formula (2) with acompound represented by the following formula (15):

provided that the symbols in the formulae have the following meanings:

A, B, D, E, G, J: each of them which may be the same or different, is—CFH— or —CF₂—;

R^(F): a perfluorinated monovalent saturated organic group;

X¹⁰: a halogen atom;

R¹: a hydrogen atom, a methyl group, a fluorine atom or atrifluoromethyl group;

X¹¹: a hydroxyl group or a halogen atom;

Y²: each of three Y²s which may be the same or different, is a hydrogenatom or a hydroxyl group;

Y³: Y³ corresponding to Y² which is a hydrogen atom, is is a hydrogenatom, and Y³ corresponding to Y² which is a hydroxyl group, is a grouprepresented by R^(F)COO— (wherein R^(F) is as defined above);

Y⁴: Y⁴ corresponding to Y³ which is a hydrogen atom, is a hydrogen atomor a fluorine atom, and Y⁴ corresponding to Y³ which is a grouprepresented by R^(F)COO—, is a group represented by R^(F)COO— (whereinR^(F) is as defined above);

Y⁵: Y⁵ corresponding to Y⁴ which is a hydrogen atom, is a hydrogen atom,Y⁵ corresponding to Y⁴ which is a fluorine atom, is a fluorine atom, andY⁵ corresponding to Y⁴ which is a group represented by R^(F)COO—, is ahydroxyl group (wherein R^(F) is as defined above); and

Y⁰: Y⁰ corresponding to Y⁵ which is a hydrogen atom, is a hydrogen atom,Y⁰ corresponding to Y⁵ which is a fluorine atom, is a fluorine atom, andY⁰ corresponding to Y⁵ which is a hydroxyl group, is a group representedby —OCOCR¹═CH₂ (wherein R¹ is as defined above) or a hydroxyl group.

2. The production process according to 1, wherein the compoundrepresented by the formula (10) is a compound represented by thefollowing formula (10A), the compound represented by the formula (12) isa compound represented by the following formula (12A), the compoundrepresented by the formula (13) is a compound represented by thefollowing formula (13A), the compound represented by the formula (2) isa compound represented by the following formula (2A), and the compoundrepresented by the formula (1) is a compound represented by thefollowing formula (1A):

provided that the symbols in the formulae are as defined above.

3. A compound represented by the following formula (1′):

provided that the symbols in the formula have the following meanings:

A, B, D, E, G, J: each of them which may be the same or different, is—CFH— or —CF₂—;

R¹: a hydrogen atom, a methyl group, a fluorine atom or atrifluoromethyl group; and

Y: a group represented by the formula —OCO—CR¹⁰═CH₂ (wherein R¹⁰ is ahydrogen atom, a methyl group, a fluorine atom or a trifluoromethylgroup), a hydrogen atom, a fluorine atom or a hydroxyl group, providedthat three Ys may be the same or different.

4. The compound according to 3, wherein in the formula (1′), A, B, E, Gand J are —CF₂—, D is —CFH—, and Y is a group represented by the formula—OCO—CR¹⁰═CH₂, a fluorine atom or a hydroxyl group, provided that threeYs may be the same or different.

5. A compound represented by the following formula (1A′):

provided that the symbols in the formula have the following meanings:

A, B, D, E, G, J: each of them which may be the same or different, is—CFH— or —CF₂—;

R¹: a hydrogen atom, a methyl group, a fluorine atom or atrifluoromethyl group; and

Y: a hydrogen atom, a fluorine atom, a hydroxyl group or a grouprepresented by the formula —OCO—CR¹⁰═CH₂ (wherein R¹⁰ is a hydrogenatom, a methyl group, a fluorine atom or a trifluoromethyl group).

6. The compound according to 5, wherein in the formula (1A′), A, B, D,E, G and J are —CF₂—, and Y is a group represented by the formula—OCO—CR¹⁰═CH₂, a fluorine atom or a hydroxyl group.

7. The compound according to 5, wherein in the formula (1A′), A, B, E, Gand J are —CF₂—, D is —CFH—, and Y is a group represented by the formula—OCO—CR¹⁰═CH₂, a fluorine atom or a hydroxyl group.

8. A compound represented by the following formula (1B):

provided that the symbols in the formula have the following meanings:

A, B, D, E, G, J: each of them which may be the same or different, is—CFH— or —CF₂—;

Y¹: a hydrogen atom, a fluorine atom or a hydroxyl group, provided thattwo Y¹s may be the same or different; and

R¹: a hydrogen atom, a methyl group, a fluorine atom or atrifluoromethyl group.

9. The compound according to 8, wherein in the formula (1B), A, B, E, Gand J are —CF₂—, D is —CFH—, and Y¹ is a hydroxyl group or a fluorineatom.

10. A compound represented by the following formula (1C):

provided that the symbols in the formula have the following meanings:

A, B, D, E, G, J: each of them which may be the same or different, is—CFH— or —CF₂—;

Y^(1F): a fluorine atom or a hydroxyl group, provided that three Y^(1F)smay be the same or different; and

R¹: a hydrogen atom, a methyl group, a fluorine atom or atrifluoromethyl group.

11. A compound represented by the following formula (1CF-1), wherein in¹HNMR spectrum (solvent: CDCl₃, standard substance: tetramethylsilane),the chemical shifts (unit: ppm) are 6.08, 6.25 and 6.57, and in ¹⁹FNMRspectrum (solvent CDCl₃, standard substance: CFCl₃), the chemical shifts(unit: ppm) are −114.7, −121.2 and −221.6:

12. A compound represented by the following formula (1CH):

provided that the symbols in the formula have the following meanings:

Y^(1F): a fluorine atom or a hydroxyl group, provided that three Y^(1F)smay be the same or different; and

R¹: a hydrogen atom, a methyl group, a fluorine atom or atrifluoromethyl group.

13. A compound represented by the following formula (1CH-1), wherein in¹HNMR spectrum (solvent: CDCl₃, standard substance: tetramethylsilane),the chemical shifts (unit: ppm) are 6.16, 6.24, 6.64 and 6.77, and in¹⁹FNMR spectrum (solvent CDCl₃, standard substance: CFCl₃), the chemicalshifts (unit: ppm) are −113.4 to −124.8, −212.5, −222.2 and −222.9:

14. A compound represented by the following formula (2A′):

provided that the symbols in the formula have the following meanings:

Y^(1F): a fluorine atom or a hydroxyl group; and

A, B, D, E, G, J: each of them which may be the same or different, is—CFH— or —CF₂—.

15. The compound according to 14, wherein A, B, E, G and J are —CF₂—,and D is —CFH—.

16. A compound represented by the following formula (2AF):

provided that Y^(1F) is a fluorine atom or a hydroxyl group.

17. A compound represented by the following formula (2BF):

provided that each Y^(1F) is a fluorine atom or a hydroxyl group.

18. The compound according to 17, wherein Y^(1F) is a fluorine atom, andin ¹⁹FNMR (solvent CD₃OD, standard substance: CFCl₃) spectrum, thechemical shifts (unit: ppm) are −117.6 to −124.4 and −221.5 to −224.5.

19. A compound represented by the following formula (13):

provided that the symbols in the formula have the following meanings:

A, B, D, E, G, J: each of them which may be the same or different, is—CFH— or —CF₂—;

R^(F): a perfluorinated monovalent saturated organic group;

Y⁴⁰: a hydrogen atom, a fluorine atom or a group represented byR^(F)COO—, and three Y⁴⁰s may be the same or different.

20. The compound according to 19, wherein A, B, D, E, G and J are —CF₂—,and Y⁴⁰ is a fluorine atom or a group represented by R^(F)COO—, providedthat three Y⁴⁰s may be the same or different.

EFFECTS OF THE INVENTION

According to the production process of the present invention, anadamantane derivative which may be a material compound of a polymerhaving excellent etching resistance and improved transparency to lighthaving a short wavelength, can be produced by an economicallyadvantageous process from a readily available material. A polymerproduced by the process of the present invention can be suitably used ase.g. a material for microprocessing technology having excellent etchingresistance and improved transparency to light having a short wavelength.

BEST MODE FOR CARRYING OUT THE INVENTION

In this specification, a compound represented by the formula (1) will bereferred to as the compound (1). The same applies to compoundsrepresented by other formulae.

The compound (1) of the present invention can be produced by a processwhich comprises subjecting a compound (10) to esterification reactionwith a compound (11) to obtain a compound (12), subjecting the compound(12) to fluorination in a liquid phase to obtain a compound (13),subjecting the compound (13) to hydrolysis or alcoholysis to obtain acompound (13), and reacting the compound (13) with a compound (15) toobtain the compound (1). Preferred embodiments regarding the symbols inthese compounds will be described below.

The compound (10) is a known compound disclosed in e.g. JP-A-63-307844.Y² in the compound (10) is a hydrogen atom or a hydroxyl group, andthree Y²s may be the same or different.

The compound (11) is a compound which can be produced by a known method.For example, the compound (11) wherein X¹⁰ is a fluorine atom can beproduced by oligomerization reaction of hexafluoropropylene, a processdisclosed in WO00/56694 by the present applicant, or the like. Further,the compound (15) is a compound which is easily available as acommercial product.

R^(F) in the formula (11) is preferably a perfluoroalkyl group, aperfluoro(partially chlorinated alkyl) group or a perfluoroalkyl groupcontaining an etheric oxygen atom, particularly preferably aperfluoroalkyl group or a perfluoroalkyl group containing an ethericoxygen atom, especially preferably a perfluoroalkyl group, furthermorepreferably such a group having from 2 to 20 carbon atoms. The number ofcarbon atoms of R^(F) is preferably such that the molecular weight ofthe compound (12) will be within a preferred molecular weight range.Usually, the number of carbon atoms of R^(F) is preferably from 2 to 20,particularly preferably from 2 to 10.

Among R^(F), examples of a perfluoroalkyl group include —CF₂CF₃,—CF₂CF₂CF₃, —CF₂CF₂CF₂CF₃, —CF(CF₃)₂, —CF₂CF(CF₃)₂, —CF(CF₃)CF₂CF₃ and—C(CF₃)₃. Examples of a perfluoro (partially chlorinated alkyl) groupinclude —CF₂CClF₂ and —CF₂CFClCF₂Cl. Specific examples of aperfluoroalkyl group containing an etheric oxygen atom include —CF(CF₃)[OCF₂CF(CF₃)_(b)]OCF₂CF₂CF₃ (wherein b is 0 or an integer of at least 1,preferably 0 or an integer of from 1 to 5) and —(CF₂)_(d)OCF₃ (wherein dis an integer of at least 1, preferably an integer of from 1 to 8.

The esterification reaction of the compound (10) with the compound (11)can be carried out under the conditions of known esterificationreactions. The lower limit of the reaction temperature for theesterification reaction is preferably −50° C., and the upper limit ispreferably +100° C. The reaction time may optionally be changeddepending upon the supply rates of the materials and the amount of thecompound. The reaction pressure is preferably from atmospheric pressureto 2 MPa (gauge pressure, hereinafter, the pressure is represented by agauge pressure).

Y³ in the compound (12) corresponds to Y². Y³ corresponding to Y² whichis a hydrogen atom is a hydrogen atom. Y³ corresponding to Y² which is ahydroxyl group is a group represented by R^(F)COO— (wherein R^(F) is asdefined above). Namely, the compound (12) is a compound having allhydroxyl groups in the compound (11) esterified, and is a mono- totetraester compound.

In the esterification reaction, the amount of the compound (11) to thecompound (10) is preferably at least 1 mol. Specifically, the amount ofthe compound (11) is preferably from 1 to 2 times by mol, particularlypreferably from 1 to 1.1 times by mol, relative to the number of mols ofhydroxyl groups in the compound (10). When the reaction is carried outin such an amount, it is possible to prevent an unreacted hydroxylgroup-containing compound from remaining in the reaction is product ofthe esterification reaction, and it is possible to avoid a side reactionin the fluorination in the subsequent step. Further, the process forpurifying the compound (12) can be simplified.

The product of the esterification reaction is preferably purified fromsuch a viewpoint that the fluorination reaction in the subsequent stepis smoothly carried out. Especially when the product of theesterification reaction contains a hydroxyl group-containing compound,it is preferred that such a compound is preliminarily removed bypurification. The purification method may, for example, be adistillation method, a method wherein the product is treated with e.g.water, followed by liquid separation, a method wherein extraction iscarried out with a suitable organic solvent, followed by distillation,silica gel column chromatography, or recrystallization.

In the esterification reaction, hydrofluoric acid (HF) will be formed,and an alkali metal fluoride (NaF or KF is, for example, preferred) or atrialkylamine may be present as a HF capturing agent in the reactionsystem. The amount of the HF capturing agent is preferably from 0.1 to10 times by mol relative to the theoretical amount of generated HF. In acase where no HF capturing agent is used, it is preferred that thereaction is carried out at a reaction temperature where HF can beevaporated, so that HF is discharged out of the reaction system asaccompanied with a nitrogen stream. Further, a method may be employedwherein the reaction is carried out without using a HF capturing agent,HF is discharged out of the reaction system as accompanied with anitrogen stream. This method is preferred from such a viewpoint that thecrude liquid may be employed as it is in the next fluorination step.

In order to let the liquid phase fluorination reaction in the subsequentstep proceed smoothly, the fluorine content of the compound (12) isadjusted to be preferably from 20 to 60 mass %, particularly preferablyfrom 25 to 55 mass %. Further, the molecular weight of the compound (12)is preferably within a range of from 200 to 1,100, particularlypreferably within a range of from 300 to 800. With the compound (12)having the fluorine content within the above specified range, thesolubility in the liquid phase at the time of the fluorination reactionwill be remarkably improved, whereby there will be a merit such that theoperation efficiency of the liquid phase fluorination reaction and thereaction yield will be improved and the economical efficiency will beexcellent.

The compound (12) can then be converted into the compound (13) byfluorination in a liquid phase. The liquid phase fluorination method ofreaction with fluorine (F₂) in a liquid phase can remarkably improve theyield of the fluorination reaction and can be employed as an industrialproduction process to carry out the process of the present invention.

The liquid phase fluorination reaction is carried out by dissolving thecompound (12) in a solvent and then reacting it with fluorine in thesolvent. The solvent is preferably a solvent inert to the fluorinationreaction. Further, the solvent is preferably a solvent in which thesolubility of the compound (12) is high, particularly preferably asolvent which is capable of dissolving at least 1 mass %, particularlypreferably at least 5 mass %, of the compound (12).

The solvent to be used for the fluorination reaction may, for example,be a known solvent used as a solvent for the liquid phase fluorination.It may, for example, be a chlorofluorocarbon such as R-113 orCF₂ClCFCl₂, perfluorotributylamine, a fluorocarbon such asperfluoro(2-butyltetrahydrofuran) or a perfluorinated acyl fluoride. Thesolvent is preferably a chlorofluorocarbon such as R-113, or aperfluorinated acyl fluoride such as the compound (11). The amount ofthe solvent is preferably at least 5 times by mass, particularlypreferably from 1×10¹ to 1×10⁵ times by mass, relative to the total massof the compound (12).

As fluorine, it is preferred to employ fluorine gas itself or fluorinegas diluted with an inert gas. The inert gas is preferably nitrogen gasor helium gas, and nitrogen gas is particularly preferred from theeconomical reason. The amount of fluorine gas in the nitrogen gas is notparticularly limited, but from the viewpoint of the efficiency, it ispreferably at least 10 vol %, particularly preferably at least 20 vol %.

Fluorine to be used for the fluorination reaction is preferablymaintained so that the amount of fluorine (F₂) to the amount of hydrogenatoms contained in the compound (12) will be always in excess byequivalent from the beginning to the end of the reaction. It ispreferred from the viewpoint of the selectivity to maintain the amountof fluorine to hydrogen atoms in the compound (12) to be at least 1.05times by equivalent (i.e. at least 1.05 times by mol), and it is furtherpreferred from the viewpoint of the selectivity to maintain it to be atleast twice by equivalent (i.e. at least twice by mol). Further, inorder to let the amount of fluorine be in excess by equivalent also atthe initiation of the reaction, it is preferred to let fluorinepreliminarily be dissolved in a sufficient amount in the solvent for thefluorination reaction to be used at the beginning of the reaction.

It is necessary to carry out the liquid phase fluorination reactionwithout breaking the ester bond in the compound (12). Accordingly, thereaction temperature is preferably from −50° C. to +100° C.,particularly preferably from −20° C. to +50° C. The reaction pressurefor the fluorination reaction is not particularly limited, and it isparticularly preferred to adjust the pressure to be from atmosphericpressure to 2 MPa from the viewpoint of the reaction yield, theselectivity and the industrial operation efficiency.

In order to let the fluorination reaction proceed efficiently, it ispreferred to add a C—H bond-containing compound such as benzene ortoluene to the reaction system, to let the compound (12) stay for a longtime in a reaction system or to carry out ultraviolet irradiation.Particularly when it is desired to fluorinate all hydrogen atoms in thecompound (12), such an operation is preferably carried out. Further,such an operation is carried out preferably at a latter stage of thefluorination reaction.

The fluorination reaction of the present invention is a reaction whereinat least one of hydrogen atoms bonded to a carbon atom in the compound(12) is substituted by a fluorine atom, and preferably, at least 50%,particularly preferably at least 90%, especially preferably at least95%, of the number of hydrogen atoms, is substituted.

In the liquid phase fluorination, HF is formed as a by-product. For thepurpose of removing HF, it is preferred to use a HF capturing agent(preferably NaF), to cool the outlet gas thereby to recover HF, or todischarge HF out of the reaction system as accompanied with an inert gassuch as nitrogen gas is The reaction product of the fluorinationreaction may be used as it is in the subsequent step or may be purifiedto a high purity product. As a purification method, a method ofdistilling a crude product under atmospheric pressure or under reducedpressure may, for example, be mentioned.

The compound (13) to be formed by the liquid phase fluorination reactionis preferably a compound having the compound (12) perfluorinated (i.e.the compound (13) wherein all of A, B, D, E, G and J are —CF₂) or acompound wherein one of hydrogen atoms bonded to carbon atoms adjacentto the carbon atom to which —OCOR^(F) is bonded of the compound (13)remained non-fluorinated, and all the remaining hydrogen atoms arefluorinated (i.e. D is —CFH—). The reason why the latter compound isformed is considered that in the compound (12), the carbonyl oxygen atomof the —OCOR^(F) group and the hydrogen atom form a hydrogen bond,whereby the hydrogen atom is less likely to be fluorinated.

In the following, a hydrogen atom bonded to a carbon atom adjacent tothe carbon atom to which —OCOR^(F) is bonded, will be referred to as a“specific hydrogen atom”. Further, compounds having all hydrogen atomsother than the specific hydrogen atom in the adamantane skeletonfluorinated will sometimes be generically referred to as a “compoundwherein hydrogen remains”.

Y⁴ in the compound (13) corresponds to Y³. Y⁴ corresponding to Y³ whichis a hydrogen atom is a hydrogen atom or a fluorine atom (preferably afluorine atom). Y⁴ corresponding to Y³ which is a group represented byR^(F)COO— (wherein R^(F) is as defined above) is a group represented bythe same R^(F)FCOO— as Y³.

The compound (13) is a novel compound provided by the novel productionprocess of the present invention. The compound (13) is useful as anintermediate for production of the compound (1) and the compound (2) asdescribed hereinafter.

Then, in the present invention, the compound (13) is subjected toalcoholysis or hydrolysis to obtain the compound (2). Alcoholysis isdecomposition reaction of the compound (13) carried out in the presenceof an alcohol, and is carried out preferably in the presence of acompound represented by the formula R^(H)—OH (wherein R^(H) is amonovalent hydrocarbon group). Further, hydrolysis is a reaction todecompose the compound (13) in the presence of water. Either reaction iscarried out usually by heating. Further, the reaction may be carried outunder any of elevated pressure, reduced pressure and atmosphericpressure.

R^(H) may be an alkyl group, a cycloalkyl group or a group wherein onehydrogen atom in adamantane becomes a bond, and such a group preferablyhas from 1 to 10 carbon atoms. In a case where the compound representedby R^(H)—OH is an alcohol, particularly preferably is a primary orsecondary alcohol or a cycloalkanol. Specific examples of the primaryalcohol include methanol, ethanol, 2-ethylhexyl alcohol and octanol,specific examples of the secondary alcohol include 2-propanol,2-buthanol and cyclohexanol, and preferred is a C₆₋₁₀ alcohol. Further,the compound represented by the formula R^(H)—OH is particularlypreferably selected from alcohols having a boiling point higher thanthat of the compound (1) as the aimed product.

Alcoholysis or hydrolysis is carried out preferably under acidic orbasic conditions. The acid is preferably hydrochloric acid, sulfuricacid or the like. The base is preferably hydroxide of an alkali metal orhydroxide of an alkaline earth metal. The hydroxide of an alkali metalis preferably NaOH, KOH or CsOH, and NaOH is particularly preferred fromeconomical viewpoint. The decomposition reaction temperature ispreferably from 50 to 300° C., particularly preferably from 100 to 250°C. The reaction pressure is not limited.

Alcoholysis or hydrolysis may be carried out in the presence of areaction solvent. The amount of the reaction solvent is preferably from0.1 to 10 times relative to the compound (10). Further, in a case wherethe compound represented by R^(H)—OH is used in excess, this compoundmay function also as a solvent.

Among the compounds (2) to be formed by the decomposition reaction ofthe compound (13), compounds wherein the number of hydroxyl groups is atleast 2 are compounds of which formation is practically confirmed by theproduction process of the present invention for the first time. Examplesof the compound (2) will be described hereinafter.

The compound (2) is a useful compound capable of being introduced intovarious useful compounds by conversion of hydroxyl groups. In thepresent invention, this compound (2) is reacted with the followingcompound (15) to obtain the compound (1). In the formula, X¹¹ ispreferably a hydroxyl group, a chlorine atom or a fluorine atom,particularly preferably a fluorine atom. R¹ is a hydrogen atom, a methylgroup, a fluorine atom or a trifluoromethyl group (hereinafter sometimesreferred to as R¹⁰).CH₂═CR¹COX¹¹   (15)

The following compounds may be mentioned as specific examples of thecompound (15):CH₂═CHCOX¹¹,CH₂═C (CH₃) COX¹¹,CH₂═CFCOX¹¹,CH₂═C (CF₃)COX¹¹.

The reaction of the compound (2) with the compound (15) may be carriedout by any one of the following methods 1 to 4.

Method 1: The method of subjecting the compound (2) and the compound(15) to azeotropic dehydration under reflux of a solvent.

Method 2: A method of subjecting the compound (2) and the compound (15)to dehydration esterification in the presence of a solvent.

Method 3: A method of subjecting the compound (2) and the compound (15)to esterification reaction in the present of a base.

Method 4: A method of converting the hydroxyl group in the compound (2)into an alkoxide, and then reacting such a compound (2) with thecompound (15) wherein Z is a chlorine atom (hereinafter referred to ascompound (15Cl)).

In the method 1, the solvent is preferably toluene, xylene or the like.As the reaction conditions for azeotropic dehydration, usual reactionconditions may be employed. The reaction temperature is preferablyadjusted to be from −78° C. to 200° C. The reaction pressure ispreferably from 0.1 to 10 MPa, and the reaction time is preferably from1 to 24 hours, particularly preferably from 3 to 6 hours. The amount ofthe solvent is preferably at least such an amount that the compound (2)has a saturated concentration, particularly preferably such an amountthat the concentration of the compound (2) is from 0.5 to 1.0 mol/liter.

In the method 2, the dehydrating agent is preferably molecular sheaves,or an acidic dehydrating agent such as anhydrous sodium sulfate,anhydrous magnesium sulfate or phosphoric anhydride. The solvent may,for example, be an ether solvent such as diethyl ether, tetrahydrofuranor dioxane; an aliphatic hydrocarbon solvent such as hexane, heptane oroctane; or an aromatic hydrocarbon solvent such as benzene, toluene orxylene. The reaction temperature in the dehydration esterificationreaction is preferably from 25° C. to (the boiling point of the solventunder the reaction pressure), particularly preferably from −78 to +200°C. The reaction pressure is preferably from 0.1 to 10 MPa, particularlypreferably atmospheric pressure. The reaction time is preferably from 1to 24 hours, particularly preferably from 3 to 6 hours. The amount ofthe solvent used is preferably at least such an amount that thesaturation solubility of the compound (2) is achieved, and usuallyparticularly preferably such an amount that the concentration of thecompound (2) is from 0.5 to 1.0 mol/liter.

In the method 3, the base may, for example, be trimethylamine,triethylamine, pyridine, or N,N-dimethylaniline. The reaction may becarried out with or without a solvent. In a case where a solvent isused, the solvent may, for example, be a halogenated hydrocarbon such asdichloromethane, chloroform, carbon tetrachloride or 1,2-dichloroethane,an ether solvent such as diethyl ether, tetrahydrofuran or dioxane; analiphatic hydrocarbon solvent such as hexane, heptane or octane; or anaromatic hydrocarbon solvent such as benzene, toluene or xylene. Theamount of the solvent is preferably such an amount that theconcentration of the compound (2) is from 0.5 to 1.0 mol/liter. Thereaction temperature is preferably from −78° C. to +100° C.,particularly preferably from −78° C. to +25° C. The reaction pressure ispreferably from 0.1 to 10 MPa. The reaction time is preferably from 1 to24 hours, particularly preferably from 1 to 3 hours.

In the method 4, the method of converting the hydroxyl group of thecompound (2) into an alkoxide is preferably carried out by a method ofreacting the compound (2) with an alkoxylation agent. The alkoxylationagent may, for example, be lithium metal, sodium metal, potassium metal,n-butyllithium, sec-butyllithium, tert-butyllithium, sodium hydroxide,sodium hydride, sodium borohydride or lithium aluminum hydride. Areaction solvent is preferably used for the reaction. The reactionsolvent may, for example, be an ether solvent such as diethyl ether,tetrahydrofuran or dioxane; an aliphatic hydrocarbon solvent such ashexane, heptane or octane; or an aromatic hydrocarbon solvent such asbenzene, toluene or xylene.

In the method 4, for the reaction of the alkoxide of the compound (2)with the compound (15), a solvent may or may not be used, but ispreferably used. In a case where a reaction solvent is used, it ispreferred to use the same solvent as the solvent used for the reactionwith the alkoxylation agent. The amount of the reaction solvent ispreferably such an amount that the concentration of the compound (15) isfrom 0.5 to 1.0 mol/liter. The reaction temperature is preferably from−78 to 100° C., particularly preferably from −78° C. to 25° C. Thereaction pressure is preferably from 0.1 to 10 MPa. The reaction time ispreferably from 1 to 24 hours, particularly preferably from 1 to 3hours.

In the method 4, the compound (15Cl) can be obtained by reacting thecompound (15) with a chlorinating agent. The chlorinating agent ispreferably, for example, thionyl chloride, phosphorus pentachloride,phosphorus trichloride, benzoyl chloride or phthaloyl chloride. Thereaction with the chlorinating agent may be carried out with or withouta solvent. In a case where a solvent is used, the solvent may, forexample, be a halogenated hydrocarbon such as dichloromethane,chloroform, carbon tetrachloride or 1,2-dichloroethane; an aliphatichydrocarbon solvent such as hexane, heptane or octane; or an aromatichydrocarbon solvent such as benzene, toluene or xylene. The amount ofthe solvent is preferably such an amount that the concentration of thecompound (15) is from 0.5 to 1.0 mol/liter.

The reaction of the compound (15) with the chlorinating agent may becarried out in the presence of a catalyst. The catalyst may, forexample, be N,N-dimethylformamide, hexamethylphosphoric triamide,pyridine or benzyltriethylammonium chloride. The reaction temperature ispreferably from 0 to 200° C., particularly preferably from 25° C. to100° C. The reaction pressure is preferably from 0.1 to 10 MPa. Thereaction time is preferably from 1 to 24 hours, particularly preferablyfrom 1 to 6 hours.

The following compound (1) to be provided by the reaction of convertingthe compound (2) is a compound which has been produced and identified bythe process of the present invention for the first time.

Among the production processes of the present invention, a process toobtain the compound (1) employing, as the compound (10) as a startingmaterial, 1,3,5-trihydroxyadamantane or 1,3,5,7-tetrahydroxyadamantaneas the starting material, is a very useful process in the process of thepresent invention employing the liquid phase fluorination method. Thisproduction process is a process which comprises subjecting the abovecompound (10A) to esterification reaction with the above compound (11)to obtain the above compound (12A), subjecting the compound (12A) tofluorination in a liquid phase to obtain the above compound (13A),subjecting the compound (13A) to hydrolysis or alcoholysis to obtain theabove compound (2A), and reacting the compound (2A) with the compound(15) in such a proportion that at least three hydroxyl groups arereacted, to obtain a compound (1A).

In production of the compound (1A), in a case where the compound (2A) isin the trihydroxy-form, the compound (1) wherein one to two hydroxylgroups remain, may be formed, and in a case where the compound (2) is inthe tetrahydroxy-form, the compound (1) wherein one to three hydroxylgroups remain, may be formed. Such a compound wherein hydroxyl groupsremain, is preferably a compound wherein all three Ys in the compound(1) are hydroxyl groups or a compound wherein two Ys are hydroxyl groupsand one Y is a fluorine atom.

In a case where the compound (2) is in the dihydroxy-form, the compound(1) wherein one hydroxyl group remains may be formed by the reaction ofthe compound (2) with the compound (15) Such a compound (1) ispreferably a compound wherein one Y⁰ is a hydroxyl group and the otherY⁰ is a fluorine atom. Such a compound wherein a hydroxyl group remainscan be produce also by changing the amount of the compound (15) to bereacted with the compound (1) (or the compound (1A)).

In the process for producing the compound (1A), it is preferred that allof A, B, D, E, G and J are —CF₂—, or one of the specific hydrogen atomsin these groups is not fluorinated and all the remaining hydrogen atomsare fluorinated (that is, one group selected from A, B, D, E, G and J is—CFH—, and the other groups are —CF₂—).

Y⁰ is a group corresponding to Y⁵. Y corresponding to Y⁵ which is ahydrogen atom is a hydrogen atom. Y corresponding to Y⁵ which is afluorine atom is a fluorine atom. Y⁵ corresponding to Y⁵ which is ahydroxyl group is a group represented by —OCOCR¹═CH₂ (wherein R¹ is asdefined above) or a hydroxyl group.

Y⁰ is preferably a group represented by the formula —OCO—CR¹═CH₂, afluorine atom or a hydroxyl group, particularly preferably a grouprepresented by the formula —OCO—CR¹═CH₂ or a fluorine atom. R¹ ispreferably a hydrogen atom or a methyl group.

The compound (1) to be provided by the present invention is thefollowing compound (1′) wherein Y is as defined above. Definition of Yis substantially the same as Y⁰. In this specification, groupsrepresented by —OCO—CR¹═CH₂ and —OCO—CR¹⁰═CH₂ will generically bereferred to as a (meth)acryloyloxy group.

Examples of the compound (1) include the following compound (1C) havingone (meth)acryloyloxy group, the following compound (1B) having two(meth)acryloyloxy groups and the following compound (1A′) having threeor four (meth)acryloyloxy groups:

In the above formulae, A, B, D, E, G, J and R¹ are as defined above.

In the compound (1C), Y^(1F) is a fluorine atom or a hydroxyl group, andthree Y^(1F)s may be the same or different. Y^(1F) is preferably afluorine atom.

In the compound (1B), Y¹ is a hydrogen atom, a fluorine atom or ahydroxyl group, and two Y¹s may be the same or different. Y¹ ispreferably each independently a fluorine atom or a hydroxyl group.Further, it is preferred that two Y¹s are fluorine atoms, two Y¹s arehydroxyl groups, or one Y¹ is a fluorine atom and the other is ahydroxyl group. In the compound (1B), in a case where any of A to J is—CFH—, or in a case where Y¹ is a fluorine atom, D is preferably —CFH—.

In the compound (1A′), Y is a hydrogen atom, a fluorine atom, a hydroxylgroup or a group represented by the formula —OCO—CR¹⁰═CH₂ (wherein R¹⁰is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethylgroup). Y is preferably a fluorine atom, a hydrogen atom or a(meth)acryloyloxy group.

Among the following compounds (1C) having one (meth)acryloyloxy group, acompound having the adamantane skeleton perfluorinated is represented bythe formula (1CF), and among the compounds (1C), a compound whereinhydrogen remains, the following compound (1CH) may be mentioned. Thesymbols in the formulae are as defined above.

The following compounds may be mentioned as specific examples of thecompound (1CF).

The following compounds may be mentioned as specific examples of thecompound (1CH).

The compound (1CF-1) and the compound (1CH-1) wherein Y^(1F) arefluorine atoms are novel compounds in that they show chemical shifts asdisclosed in Examples under ¹HNMR and ¹⁹FNMR measurement conditionsdisclosed in Examples of this specification.

Among the compounds (1B) having two (meth)acryloyloxy groups, a compoundhaving the adamantane skeleton perfluorinated is represented by theformula (1BF), and among the compounds (1B), as the compound whereinhydrogen remains, the following compound (1BH) may be mentioned. Thesymbols in the formulae are as defined above.

The following compounds may be mentioned as specific examples of thecompound (1BF).

The following compounds may be mentioned as specific examples of thecompound (1BH).

The compound (1B) is a novel compound in that its production process isprovided by the production process of the present invention and it isidentified for the first time.

The compound (1A′) having three or four (meth)acryloyloxy groups is thesame as the compound (1A) obtained by the above production process.Among the compounds (1A′), a compound having the adamantane skeletonperfluorinated is preferably the following compound (1AF), and among thecompounds (1A′), as the compound wherein hydrogen remains, the followingcompound (1AH) is preferred.

In the above, R¹ is as defined above, and Y^(F)s are such that twoY^(F)s are groups represented by the formula —OCO—CR¹⁰═CH₂ and the otherone Y^(F) is a fluorine atom or a hydrogen atom (Y^(F) is preferably afluorine atom), or four Y^(F)s are groups represented by —OCO—CR¹⁰═CH₂.

The following compounds may be mentioned as specific examples of thecompound (1AF).

The following compounds may be mentioned as specific examples of thecompound (1AH).

The present invention further provides the above compound (13) which isuseful as an intermediate for production of the compound (1). In thefollowing formulae, R^(F) is as defined above, and its preferredembodiments are also as defined above.

The following compounds may be mentioned as specific examples of thecompound (13) having the adamantane skeleton perfluorinated.

The following compounds may be mentioned as specific examples of thecompound (13) in the case of the compound wherein hydrogen remains.

The following compounds may be mentioned as specific examples of thecompound (2) having one hydroxyl group among the compounds (2) as anintermediate for production of the compound (1).

Among the compounds (2), compounds having two to four hydroxyl groupsare novel compounds in that their production process is provided by theproduction process of the present invention and they are identified forthe first time.

Among the compounds (2), as a compound having 3 or 4 hydroxyl groups,the following compound (2A′) is preferred. In the following, Y^(1F) is afluorine atom or a hydroxyl group, and each of A to J is —CFH— or —CF₂—.

Among the compounds (2A′), a compound having the adamantane skeletonperfluorinated is represented by the following formula (2AF), and thecompound wherein hydrogen remains is represented by the followingformula (2AH). The symbols in the following formulae are as definedabove, and it is preferred that A, B, E, G and J are —CF₂— and D is—CFH—. A composition comprising the compound (2AF) and the compound(2AH) is also a novel composition.

The following compounds may be mentioned as specific examples of thecompound (2AF).

The following compounds may be mentioned as specific examples of thecompound (2AH) wherein hydrogen remains.

The following compound (2BF) may be mentioned as a compound having twohydroxyl groups among the compounds

Further, the compound (2CF-1) which is in the perfluorinated monohydroxyform, is a compound which shows chemical shifts under ¹HNMR and ¹⁹FNMRmeasurement conditions as disclosed in Examples of this specification.

The compound (1) provided by the present invention is a compound havinga (meth)acryloyl group which is a polymerizable unsaturated group. Apolymer to be obtained from this compound has a fluorinated adamantanestructure in its side chains. Since the fluorinated adamantane structureis a very rigid structure, a hard polymer with a small volume changewill be obtained. Further, a polymer having various functions derivedfrom fluorine atoms will be provided.

Further, according to the present invention, a partially fluorinatedcompound (1) will be provided. The proportion of hydrogen atoms in thepartially fluorinated compound (1) will easily be changed by adjustingthe reaction conditions for the fluorination reaction. Further, by thepresence of the specific hydrogen atom which is hardly fluorinated, itis also possible to produce the compound (1) wherein the atomic weightof such a hydrogen atom or the bonding position of the hydrogen atom isspecified. A polymer obtained by polymerizing the compound (1)containing hydrogen atoms differs in the refractive index and thesolubility in a solvent from a polymer obtained by polymerizing theperfluorinated compound (1). Accordingly, the content of hydrogen atomsshould be adjusted depending upon desired physical properties.

The polymer obtained by polymerizing the compound (1) may be a polymerobtained by polymerizing only the compound (1) or a polymer obtained bypolymerizing the compound (1) with another polymerizable compoundcopolymerizable with the compound (1) (hereinafter referred to as acomonomer). The type of the comonomer may be properly changed dependingupon the purpose of use of the polymer.

The polymer provided by the present invention is a material applicableto fine photolithographic material, optical adhesives, etc. For example,as photolithographic material, a high level of etching resistance willbe provided. The reason is considered to be such that in an adamantaneskeleton having a structure wherein cyclic compounds are bonded to oneanother, even if part of bonds is broken by a laser beam, the compoundhardly undergoes decomposition, and that C—F structures are less likelyto undergo decomposition than C—H structures, and the carbon-carbonbonds are stronger.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific Examples.

In Examples, 1,1,2-trichloro-1,2,2-trifluoroethane will be referred toas R-113, and dichloropentafluoropropane as R-225. As R-225, a mixedproduct of CF₃CF₂CHCl₂ and CF₂ClCF₂CHFCl was used. Gas chromatographywill be referred to as GC, and the results in the GC analyses are shownby the peak area ratios. Gas chromatography mass spectrometry will bereferred to as GC-MS. The pressure in Examples is shown by a gaugepressure.

Example 1 Example for preparation of1,3,5-trisacryloyloxy(fluoroadamantane) Example 1-1 Esterification of1,3,5-trihydroxyadamantane

1,3,5-trihydroxyadamantane (5.15 g) was dissolved in dimethylacetamide(55 mL) and charged into an autoclave, perfluoroisobutyloyl fluoride (86g) was fed dividedly four times, followed by reaction at 25° C. for 64hours. After purging with nitrogen gas, the reaction mixture wasneutralized with a sodium bicarbonate water, followed by extraction withR-225, and the organic layer was concentrated and left to stand, and theprecipitated crystals were subjected to filtration and recovered (14.9g). The crystals (2.3 g) were recovered from the filtrate. The yield was80%. The obtained crystals were put together and recrystallized fromR-225/hexane (2/1 volume ratio) to obtain colorless crystals of1,3,5-tris(perfluoroisobutyloyloxy)adamantane with a recovery rate of50%.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 2.21 (6H),2.59 to 2.75 (7H).

¹³C-NMR (100.53 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 28.9, 37.8,43.0, 84.4, 86.7, 88.9, 118.7, 156.1).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −74.7(18F), −180.7 (3F).

IR(KBr): 1,772, 1,785 cm⁻¹.

Example 1-2 Fluorination of1,3,5-tris(perfluoroisobutyloyloxy)adamantane

R-113 (312 g) was charged into a 500 mL autoclave made of nickel,stirred and maintained at 25° C. At a gas outlet of the autoclave, acondenser maintained at 20° C., a NaF pellet packed layer and acondenser maintained at −10° C. were installed in series. Further, fromthe condenser maintained at −10° C., a liquid-returning line wasinstalled to return the condensed liquid to the autoclave. Afternitrogen gas was blown to the autoclave at 25° C. for one hour, fluorinegas diluted to 20% with nitrogen gas (hereinafter referred to as 20%diluted fluorine gas) was blown at 25° C. at a flow rate of 5.47 L/h forone hour. Then, while the 20% diluted fluorine gas was blown at the sameflow rate, a solution having the crystals (5 g) of1,3,5-tris(perfluoroisobutyloyloxy)adamantane obtained in Example 1-1dissolved in R-113 (100 g) was injected over a period of 2.8 hours.

Then, while the 20% diluted fluorine gas was blown at the same flow rateand the pressure of the reactor was maintained at 0.15 MPa, a R-113solution having a benzene concentration of 0.01 g/mL was injected in anamount of 9 mL while the temperature was raised from 25° C. to 40° C.,whereupon the benzene solution inlet of the autoclave was closed, andstirring was continued for 0.3 hour.

Then, while the internal pressure of the reactor was maintained at 0.15MPa and the internal temperature of the reactor was maintained at 40°C., 6 mL of the benzene solution mentioned above was injected, thebenzene solution inlet of the autoclave was closed, and stirring wascontinued for 0.3 hour. The same operation was repeated three times. Thetotal amount of benzene injected was 0.33 g, and the total amount ofR-113 injected was 33 mL.

Further, stirring was continued for one hour while the 20% dilutedfluorine gas was blown at the same flow rate. Then, the internalpressure of the reactor was adjusted to atmospheric pressure andnitrogen gas was blown for one hour. As a result of ¹H-NMR and ¹⁹F-NMRanalysis of the product, fluorinated product of1,3,5-tris(perfluoroisobutyloyloxy)adamantane was formed as the mainproduct. According to GC analysis, the selectivity of1,3,5-tris(perfluoroisobutyloyloxy)perfluoroadamantane which was acompletely fluorinated product was 4%, the selectivity of2-hydro-1,3,5-tris(perfluorobutyloyloxy)perfluoroadamantane was 80%, andthe selectivity of 1,3,5-tris(perfluoroisobutyloyloxy)fluoroadamantanehaving at least two hydrogen atoms was 15%. The NMR spectrum data of theproduct are shown below.

1,3,5-Tris(perfluoroisobutyloyloxy)perfluoroadamantane

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −74.7,−106.1 to −121.1, −178.7, −180.1, −217.8 to −221.7.

2-Hydro-1,3,5-tris(perfluoroisobutyloyloxy)perfluoroadamantane

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 7.72 to 7.92.¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −74.7,−106.1 to −121.1, −178.7, −180.1, −218.3, −219.1, −219.7.

Example 1-3 Decomposition reaction of fluorinated1,3,5-tris(isobutyloyloxy)adamantane

The product obtained in Example 1-2 was concentrated and added to anethanol solution (70 mL) of sodium hydroxide (5 g), and the precipitatedsolid was dissolved in R-225, followed by reflux with heating for 5hours. Stirring was carried out at 25° C. for 19 hours, followed byreflux with heating further for 7 hours. After the reaction solution wasleft to cool, it was concentrated to obtain an orange mixture of solidand liquid. The mixture was neutralized with 3M hydrochloric acid andwashed with R-225, the aqueous layer was concentrated, water wascompletely removed, followed by extraction with ethanol, and the extractwas concentrated to obtain a solid (0.8 g). The solid was analyzed andas a result, formation of perfluoro(1,3,5-trihydroxyadamantane) and2-hydro-perfluoro(1,3,5-trihydroxyadamantane) was confirmed. NMRspectrum data of the products are shown below.

Perfluoro(1,3,5-trihydroxyadamantane)

¹⁹F-NMR (282.7 MHz, solvent: CD₃OD, standard: CFCl₃)δ (ppm): −117.2 to−124.4 (m), −220.6 to −222.2 (m).

2-Hydro-perfluoro(1,3,5-trihydroxyadamantane)

¹H-NMR (300.4 MHz, solvent: CD₃OD, standard: CD₃OD) δ (ppm): 3.7.¹⁹F-NMR (282.7 MHz, solvent: CD₃OD, standard: CFCl₃) δ (ppm): −117.2 to124.4 (m), −220.5 (m), −221.5 (m), −223.4 (m).

Example 1-4 Acryloylation of fluoro(1,3,5-trihydroxyadamantane)

The product (0.42 g) obtained in Example 1-3 was stirred in diethylether (10 mL), and after cooling with ice water, triethylamine (0.42 g)and acryloyl chloride (0.33 g) were added. Then, stirring was carriedout at 25° C. overnight, the solid was subjected to filtration, and thenthe filtrate was concentrated, and the residue was isolated by columnchromatography to obtain a product (0.06 g). The product was analyzedand as a result, formation of 1,3,5-trisacryloyloxy(perfluoroadamantane)was confirmed. Further, formation of2-hydro-1,3,5-trisacryloyloxy(perfluoroadamantane) was confirmed. TheNMR spectrum data of the products are shown below.

1,3,5-Trisacryloyloxy(perfluoroadamantane

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 6.06 to 6.65(m). ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm):−112.3 to −121.9 (m), −219.2 (m).

2-Hydro-1,3,5-trisacryloyloxy(perfluoroadamantane)

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 6.06 to 6.65(m). ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm):−112.3 to −121.9 (m) −219.4 (m), −220.3 (m), −220.8 (m).

Example 2 Example for preparation of1,3,5,7-tetrakisacryloyloxy(fluoroadamantane)

The same reactions as in Examples 1-1 to 1-4 are carried out except that1,3,5-trihydroxyadamantane used in Example 1-1 is changed to1,3,5,7-tetrahydroxyadamantane, whereupon formation of1,3,5,7-tetrakisacryloyloxy(perfluoroadamantane) is confirmed. Further,formation of 2-hydro-1,3,5,7-tetrakisacryloyloxy(perfluoroadamantane) isconfirmed.

Example 3 Example for preparation of 1-acryloyloxy(fluoroadamantane)

Example 3-1 Example for preparation of compound (12C-1) byesterification reaction of 1-hydroxyadamantane

1-Adamantanol (3.09 g, 20.3 mmol) and sodium fluoride (0.95 g, 22.6mmol) were put into a 50 mL round-bottomed flask, andCF₃(CF₂)₂OCF(CF₃)COF (9.94 g, 29.9 mmol) was dropwise added at 25° C.with stirring. After completion of the dropwise addition, stirring wascarried out while the temperature was raised to 50° C., and stirring wascontinued for 9 hours while the internal temperature was maintained atfrom 45 to 50° C. R-225 was added for dilution, then sodium fluoride wasremoved by filter paper, followed by washing with water, whereuponmagnesium sulfate was added, and the mixture was left to standovernight. Magnesium sulfate was removed by filtration, and the filtratewas concentrated by an evaporator to obtain 8.80 g of a crude liquid. Asa result of analyses by GC and NMR, it was confirmed that compound(12C-1) was formed at a selectivity of 99.8% and in a yield of 93.2%.The spectrum data of the compound (12C-1) are as follows.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.69 (s, 6H),2.15 (s, 6H), 2.24 (s, 3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −79.8 to−80.4 (1F), −81.7 (3F), −82.4 (3F), −86.4 to −87.0 (1F), −130.2 (2F),−131.7 (1F).

Example 3-2 Example for preparation of compound (13CF-1) and compound(13CH-1) by fluorination reaction of 1-hydroxyadamantane esterified atthe 1-position

The same autoclave as in Example 1-2 was prepared, and after blowing the20% diluted fluorine gas at 25° C. at a flow rate of 13.22 L/hr for 30minutes, the internal pressure of the autoclave was raised to 0.15 MPa,whereupon the same gas was blown further for 30 minutes. Then, while the20% diluted fluorine gas was blown at the same flow rate, a solutionhaving the compound (12C-1) (5 g) obtained in Example 2-1 dissolved inR-113 (100 g), was injected over a period of 4.2 hours.

A reaction was carried out under the same conditions as in Example 1-2(provided that the benzene injection was carried out three times, andthe total amount of benzene injected was 0.33 g, and the total amount ofR-113 injected was 33 mL). After the reaction, the internal pressure ofthe reactor was adjusted to atmospheric pressure, and nitrogen gas wasblown for one hour. The product was analyzed by ¹⁹F-NMR, whereby it wasconfirmed that compound (13CF-1) was contained in a yield of 83%. Theproduct also contained compound (13CH-1).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −79.4 to−80.1 (1F), −81.7 to −82.2 (6F), −87.2 to −88.1 (1F), −113.5 to −124.5(12F), −130.1 (2F), −131.2 (1F), −220.0 to −223.2 (3F).

Example 3-3 Example for preparation of compound (2CF-1) and compound(2CH-1) by hydrolysis

The fluorination product solution (8.4 g) obtained in Example 3-2 wascharged into a 50 mL round-bottomed flask, and an ethanol solutioncontaining 10 wt % of is sodium hydroxide was dropwise added withstirring in a water bath. The temperature was slowly raised to 70° C.while stirring was continued, and after three hours, the stirring wasstopped. A diluted HCl aqueous solution was slowly dropwise added untilthe liquid became acidic, and then t-butyl methyl ether was addedthereto, followed by extraction twice. The obtained organic layer wasconcentrated by an evaporator and subsequently sufficiently evaporatedto dryness by a vacuum pump to recover a pale yellow powder (7.3 g). Asa result of analysis by GC, GC-MS and ¹⁹F-NMR, it was confirmed thatcompound (2CF-1), compound (2CH-1) and CF₃(CF₂)₂OCF(CF₃)COONa salt werecontained in a ratio of compound (2CF-1): compound (2CH-1):CF₃(CF₂)₂OCF(CF₃)COONa salt=1.7:1.0:3.0 (molar ratio).

Compound (2CF-1): ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ(ppm): −121.5 (12F), −222.8 (3F).

Compound (2CH-1): ¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ(ppm): 5.24 (d, J_(HF)=48.1 Hz, 1H) ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃,standard: CFCl₃) δ (ppm): −119.2 to 125.2 (10F), −213.5 (1F), −222.4(1F), −223.5 (1F), −224.8 (1F).

Example 3-4 Example for preparation of compound (1CF-1) and compound(1CH-1) by 1-acryloylation

The powder (1.1 g) obtained in Example 3-3 was charged into a 50 mLround-bottomed flask, and diethyl ether (2.5 g) and triethylamine (0.2g) were added thereto. This flask was put in an ice bath, and acrylicacid chloride (0.16 g) was slowly dropwise added thereto with stirring.Simultaneously with the dropwise addition, white precipitates wereformed in the flask. After the entire acrylic acid chloride was dropwiseadded, the ice bath was removed, followed by stirring at 25° C. for 10hours. This reaction solution was washed with deionized water to removethe formed white precipitates, and the organic layer was separated. As aresult of analysis by GC, GC-MS and ¹⁹F-NMR, it was confirmed thatcompound (1CF-1), compound (1CH-1) and unreacted compound (2CF-1) weremain components. As determined by GC analysis, the reactivity of thecompound (1CF-1) was 56%, the reactivity of the compound (1CH-1) was 97%and the selectivity of both the compounds (1CF-1) and (1CH-1) was 93%.The NMR spectrum data of these compounds are shown below.

Compound (1CF-1): ¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ(ppm): 6.08 (dd, J_(HF)=1.5, 10.2 Hz, 1H), 6.25 (dd, J_(HF)=10.2, 16.5Hz, 1H), 6.57 (dd, J_(HF)=1.5, 16.5 Hz, 1H). ¹⁹F-NMR (282.7 MHz,solvent: CDCl₃, standard: CFCl₃) δ (ppm): −114.7 (6F), −121.2 (6F),−221.6 (3F).

Compound (1CH-1): ¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ(ppm): 6.16 (dd, J_(HF)=1.5, 10.5 Hz, 1H), 6.24 (dd, J_(HF)=10.5, 16.2Hz, 1H), 6.64 (dd, J_(HF)=1.5, 16.2 Hz, 1H), 6.77 (dq, J_(HF)=45.4, 6.3Hz, 1H). ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ(ppm):−113.4 to −124.8 (10F), −212.5 (1F), −222.2 (2F), −222.9 (1F).

Example 4 Acryloylation of fluoro(1,3,5-trihdyroxyadamantane)

The product (0.26 g) obtained in Example 1-3 was stirred in diethylether (5 mL), followed by cooling with ice water, and triethylamine(0.34 g) and acryloyl chloride (0.089 g) were added. Then, stirring wascarried out at 25° C. overnight, and the solid was removed byfiltration, the filtrate was concentrated, and residual products wereseparated by column chromatography to obtain a product (0.06 g). As aresult of analysis of the product, formation of1-acryloyloxy-3,5-dihydroxy(perfluoroadamantane) and1,3-diacryloyloxy-5-hydroxy(perfluoroadamantane) was confirmed. Further,formation of 2-hydro-1-acryloyloxy-3,5-dihydroxy(perfluoroadamantane)and 2-hydro-1,3-diacryloyloxy-5-hyroxy(perfluoroadamantane) wasconfirmed. NMR spectrum data of the products are shown below.

1-Acryloyloxy-3,5-dihydroxy(perfluoroadamantane)

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 6.08 (dm,J=10.5 Hz), 6.21 (dd, J=10.5, 16.9 Hz), 6.51 (dm, J-16.9 Hz). ¹⁹F-NMR(282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −115.3 to −122.5(m), −221 to −222 (m).

2-Hydro-1-acryloyloxy-3,5-dihydroxy(perfluoroadamantane)

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 6.08 (dm,J=10.5 Hz), 6.21 (dd, J=10.5, 16.9 Hz), 6.34 (dm, J=48 Hz), 6.51 (dm,J=16.9 Hz). ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ(ppm): −112.7 to −125.7 (m), −221.7 (m), −222.5 (m).

1,3-Diacryloyloxy-5-hydroxy(perfluoroadamantane)

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 6.06 to 6.65(m). ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm):−111.9 to −121.9 (m), −218.8 to −222.3 (m).

2-Hydro-1,3-diacryloyloxy-5-hydroxy(perfluoroadamantane)

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 6.06 to 6.65(m). ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm):−113.6 to −121.9 (m), −219.4 (m), −220.5 (m), −222.1 (m).

Example 5 Example for preparation of 1,3-diacryloyloxy(fluoroadamantane)

Example 5-1 Esterification reaction of 1,3-dihydroxyadamantane

1,3-dihydroxyadamantane (2.01 g, 11.9 mmol) and 1.51 g (35.9 mmol) ofsodium fluoride were put in a 50 mL round-bottomed flask, and R-225 wasadded, followed by stirring in a suspension state. CF₃(CF₂)₂OCF(CF₃)COF(11.23 g, 33.8 mmol) was dropwise added at room temperature whilestirring was continued. After completion of the dropwise addition,stirring was carried out while the temperature was raised to 70° C., andstirring was continued for 12 hours while the internal temperature wasmaintained at from 60 to 65C. R-225 was added for dilution, and sodiumfluoride was removed by a filter paper, and the obtained solution wasconcentrated by an evaporator to remove R-225 and the excessCF₃(CF₂)₂OCF(CF₃)COF. This concentrated liquid was subjected toliquid-liquid separation twice with a sodium bicarbonate water andR-225, and the obtained organic layer was washed with water twice,magnesium sulfate was added thereto, and the organic layer was left atrest overnight. Magnesium sulfate was removed by filtration, and theorganic layer was concentrated by an evaporator and a vacuum pump toobtain a colorless solution (8.28 g). As a result of analysis by GC andNMR, it was confirmed that compound (12B-1) was obtained with aselectivity of 95.4% and a yield of 83.4%.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.65 (s, 2H),2.09 to 2.26 (m, 8H), 2.51 (s, 4H). ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃,standard: CFCl₃) δ (ppm): −78.9 to −79.4 (2F), −81.1 (6F), −81.8 (6F),−86.0 to −86.5 (2F), −129.2 (4F), −130.9 (2F).

Example 5-2 Fluorination of compound (12B-1)

Into a 500 mL autoclave made of nickel, R-113 (312 g) was introduced,stirred and maintained at 25° C. At a gas outlet of the autoclave, acondenser maintained at 20° C., a NaF pellet packed layer and acondenser maintained at −10° C. were installed in series. Further, fromthe condenser maintained at −10° C., a liquid-returning line wasinstalled to return the condensed liquid to the autoclave. Afternitrogen gas was blown to the autoclave at room temperature for onehour, fluorine gas diluted to 20% with nitrogen gas (hereinafterreferred to as 20% diluted fluorine gas) was blown at room temperatureat a flow rate of 10.6 L/h for 30 minutes, and then the internalpressure of the autoclave was raised to 0.15 MPa, and the 20% dilutedfluorine gas was blown further for 30 minutes. Then, while the internalpressure of the reactor was maintained at 0.15 MPa and the 20% dilutedfluorine gas was blown at the same flow rate, a solution having theproduct (4.7 g) obtained in Example 5-1 dissolved in R-113 (94.3 g) wasinjected over a period of 2.6 hours.

Then, while the 20% diluted fluorine gas was blown at the same flow rateand the internal pressure of the autoclave was maintained at 0.15 MPa, aR-113 solution having a benzene concentration of 0.01 g/mL was injectedin an amount of 9 mL while the temperature was raised from 25° C. to 40°C., whereupon the benzene solution inlet of the autoclave was closed,and stirring was continued for 0.3 hour.

Then, while the internal pressure of the reactor was maintained at 0.15MPa and the internal temperature of the reactor was maintained at 40°C., the above benzene solution (6 mL) was injected, whereupon thebenzene solution inlet of the autoclave was closed, and stirring wascontinued for 0.3 hour. The same operation was further repeated threetimes. The total amount of benzene injected was 0.34 g and the totalamount of R-113 injected was 33 mL.

Further, stirring was continued for one hour while the 20% dilutedfluorine gas was blown at the same flow rate. Then, the internalpressure of the reactor was adjusted to atmospheric pressure, andnitrogen gas was blown for one hour. The product was analyzed by GC-MS,¹H-NMR and ¹⁹F-NMR and as a result, it was confirmed to contain compound(13BF-1) with a yield of 55%. Further, compound (13BH-1) was containedwith a yield of 27%. Other main components among components werecompounds having at least two hydrogen atoms present in the adamantaneskeleton.

¹⁹F-NMR of compound (13BF-1) (282.7 MHz, solvent: CDCl₃, standard:CFCl₃) δ (ppm): −79.3 to −80.4 (2F), −81.8 to −82.4 (12F), −87.2 to−88.2 (2F), −109.2 to −121.4 (12F), −130.1 (4F), −129.7 to −131.9 (2F),−219.1 to −220.7 (2F).

¹H-NMR of compound (13BH-1) (300.4 MHz, solvent: CDCl₃, standard: TMS) δ(ppm): 7.81 (d, J_(HF)=43.6 Hz, 1H).

¹⁹F-NMR of compound (13BH-1) (282.7 MHz, solvent: CDCl₃, standard:CFCl₃) δ (ppm): −79.3 to −80.4 (2F), −81.8 to −82.4 (12F), −87.2 to−88.2 (2F), −109.2 to −121.4 (10F), −130.1 (4F), −129.7 to −131.9 (2F),−218.5 to −221.3 (3F).

Example 5-3 Decomposition reaction of compound (2BF-1) and compound(2BH-1)

The solution (11.8 g) of the products obtained in Example 5-2 wascharged into a 100 mL round-bottomed flask, and a methanol solution (24g) containing 15 wt % of sodium hydroxide was dropwise added thereto.The flask was heated while stirring was continued, followed by refluxfor 11 hours, and then the flask was left to cool. A diluted HCl aqueoussolution was slowly dropwise added until the liquid became neutral, andt-butyl methyl is ether was added, followed by extraction three times.The obtained organic layer was concentrated by an evaporator andsubsequently sufficiently evaporated to dryness by a vacuum pump torecover a pale yellow powder (3.8 g). As a result of analysis by¹⁹F-NMR, the powder was confirmed to contain compound (2BF-1), compound(2BH-1) and CF₃(CF₂)₂OCF(CF₃)COONa salt.

¹⁹F-NMR of compound (2BF-1) (282.7 MHz, solvent: CD₃OD, standard: CFCl₃)δ (ppm): −117.6 to −124.4, −221.5 to −224.5.

¹H-NMR of compound (2BH-1) (300.4 MHz, solvent: CDCl₃, standard: TMS) δ(ppm): 4.95 (dm, J_(HF)=47.8 Hz, 1H).

¹⁹F-NMR of compound (2BH-1) (282.7 MHz, solvent: CD₃OD, standard: CFCl₃)δ (ppm): −118.1 to −123.9 (10F), −221.6 (1F), −222.5 (1F), −223.5 (dm,J=48 Hz, 1F).

Example 5-4 Acryloylation of compound (2BF-1) and compound (2BH-1)

The solid (3.9 g) obtained in Example 5-3 was charged into a 100 mLround-bottomed flask, and t-butyl methyl ether (30 mL) and triethylamine(2.03 g) were added thereto. This flask was put in an ice bath, andacrylic acid chloride (1.63 g) was slowly dropwise added thereto withstirring. Simultaneously with the dropwise addition, white precipitateswere formed in the flask. After the entire acrylic acid chloride wasdropwise added, the ice bath was removed, followed by stirring at 25° C.for 19 hours. Part of this reaction solution was concentrated andanalyzed by NMR, whereby formation of compound (1BF-1), compound(1BH-1), compound (1CF-2) and compound (1CH-2) was confirmed. Further,unreacted compound (2CF-1) was also contained. As determined by GCanalysis, the reactivity of the compound (1CF-2) was 56%, the reactivityof the compound (1CH-2) was 97%, and the selectivity of both thecompounds (1CF-2) and (1CH-2) was 93%. NMR spectrum data of the reactionsolution are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 6.09 to 6.73(m), 8.02 (dt, J=42, 6.6 Hz). ¹⁹F-NMR (282.7 MHz, solvent: CDCl₃,standard: CFCl₃) δ (ppm): −113.5 to −121.8 (m), −219.6 (m), −221.1 (m),−221.5 (m).

INDUSTRIAL APPLICABILITY

According to the production process of the present invention, adamantanederivates which can be material compounds of a polymer excellent inetching resistance and having improved transmittance to light having ashort wavelength, can be produced by an economically advantageousprocess from readily available materials.

A polymer produced by the process of the present invention may besuitably used e.g. as materials for microprocessing technology which areexcellent in etching resistance and have improved transmittance to lighthaving a short wavelength.

The entire disclosure of Japanese Patent Application No. 2004-178331filed on Jun. 16, 2004 including specification, claims and summary isincorporated herein by reference in its entirety.

1. A compound represented by the following formula (2A″)

wherein Y^(1F) is a fluorine atom or a hydroxyl group.